Synthesis Of Nano Materials

Subject: Methods and Techniques of Experimental Physics

By
Dr. Hafiz Naeem-ur-Rahman
Introduction

 Nanomaterials describe, in principle, materials of which a single

unit is sized (in at least one dimension) between 1 and 1000
nanometres.
 Biological systems often feature natural, functional
nanomaterials. The structure of foraminifera and viruses
(capsid), the wax crystals covering a lotus or nasturtium leaf,
spider and spider-mite silk are few examples of natural
nanomaterials.
Introduction

 Natural inorganic nanomaterials occur through crystal growth in

the diverse chemical conditions of the earth's crust. For example
clays display complex nanostructures due to anisotropy of their
underlying crystal structure, and volcanic activity can give rise to
opals, which are an instance of a naturally occurring photonic
crystals due to their nanoscale structure.
Photonic Crystals

 A photonic crystal is a periodic optical nanostructure that

affects the motion of photons. They are used to manipulate
light flow. Used to form colour changing paints and inks.
Synthesis

 Includes two methods

 Bottom Up Approach
 Top Down Approach
Top Down

 Start with bulk material and “cut away material “ to make

what you want.
 Examples:
 ATTRITION: In attrition, macro- or micro-scale particles
are ground in a ball mill, a planetary ball mill, or other size-
reducing mechanism. The resulting particles are air classified
to recover nanoparticles.
Top Down

 Lithography : It is a wafer scale process to prepare

homogenous 1D,2D or 3D nanomaterials.
 The method combines the advantages of both top down and
bottom up approaches and is a two step process :
 The preparation of colloidal crystal mask (CCM) made of nano
spheres.
 The decomposition of desired material through the mask.
 The mask is then removed and the layer keeps the ordered pattern
of the mask interstices.
Bottom Up

 Building what you want by assembling it from building blocks

(Such as atoms and molecules).
 Controlled
 Controlled Processes involve the controlled delivery of the
constituent atoms or molecules to the site(s) of nanoparticle
formation such that the nanoparticle can grow to a
prescribed sizes in a controlled manner.
Bottom Up

 Bottom up approach are further classified into 1.) Gas

(Vapor) Phase Fabrication: Pyrolysis
2.) Liquid Phase Fabrication: Solvothermal Reaction, Sol-
gel.
Bottom Up Approach Types
HIGH ENERGY BALL
MILLING

Simplest method of making nanoparticle in the form

of powder
Various types of mills
• Planetary
• Vibratory
• Rod
• Tumbler
Consists of a container filled with hardened steel or
tungsten carbide balls
Material of interest is fed as flakes
2:1 mass ratio of balls to materials
Container may be filled with air or
inert gas
Containers are rotated at high speed around a central
axis
Material is forced to the walls and pressed against the
walls
Control the speed of rotation and duration of milling-
grind material to fine powder( few nm to few tens
of nm)
Some materials like Co, Cr, W, Al-Fe, Ag-Fe etc are
made nanocrystalline using ball mill.
 MELT MIXING

To form or arrest nanoparticles in glass

Glass – amorphous solid, lacking symmetric
arrangement of atoms/molecules
Metals , when cooled at very high cooling rates (10⁵-
10⁶ K/s) can form amorphous solids- metallic
glasses
Mixing molten streams of metals at high velocity with
turbulence- form nanoparticles
Ex: a molten stream of Cu-B and molten stream of Ti
form nanoparticles of TiB₂
Pyrolysis

 In pyrolysis, is a process in which a thin film is deposited by spraying a

solution on a heated surface, where the constituents react to form a chemical
compound. The chemical reactants are selected such that the products other
than the desired compound are volatile at the temperature of deposition

 The advantages of vapor phase pyrolysis include it being a simple process,

cost effective, a continuous operation with high yield.
Solvothermal Process

 Precursors are dissolved in hot solvents (e.g., n-butyl alcohol) and

solvent other than water can provide milder and friendlier
reaction conditions. If the solvent is water then the process is
referred to as hydrothermal method.
 It is synthesis method for growing for crystals from a non aqueous
solution in a autoenclave (a thick walled steel vessel) at high
temperature ( 400 deg.C) and pressure.
Sol-Gel

 The sol-gel process is a wet-chemical technique (also known as

chemical solution deposition) widely used recently in the fields
of materials science and ceramic engineering.
Steps Include

 Formation of stable sol.

 Gelation
 Gel aging into a solid mass. This causes contraction of the gel
network, also phase transformations and Ostwald ripening.
 Drying of the gel to remove liquid phases. This can lead
to fundamental changes in the structure of the gel.
COLLOIDS AND COLLOIDS IN
SOLUTION
 Nanoparticles synthesized by chemical methods form “colloids”
 Two or more phases (solid, liquid or gas) of same or different materials co-exist with the
dimensions of at least one of the phases less than a micrometre
 May be particles, plates or fibres
 Nanomaterials are a subclass of colloids, in which the dimensions of colloids is in the
nanometre range
SYNTHESIS OF METAL NANOPARTICLES
BY COLLOIDAL ROUTE

Reduction of some metal salt or acid

Highly stable gold particles can be obtained by
reducing chloroauric acid (HAuCl₄)with tri sodium
citrate(Na₃C₆H₅O₇)
HAuCl₄+ Na₃C₆H₅O₇ Au ⁺+ C₆H₅O₇⁻+ HCl+3 NaCl Metal
gold nanoparticles exhibit intense
red, magenta etc., colours depending upon the
particle size
Gold nanoparticles can be stabilised by repulsive
Coloumbic interactions
Also stabilised by thiol or some other capping
molecules
In a similar manner, silver, palladium, copper and few
other metal nanoparticles can be synthesized.
 SYNTHESIS OF SEMI-CONDUCTOR
NANOPARTICLES BY COLLOIDAL ROUTE

Wet chemical route using appropriate salts

Sulphide semiconductors like CdS and ZnS can be
synthesized by coprecipitation
To obtain Zns nanoparticles, any Zn salt is dissolved in
aqueous( or non aqueous) medium and H₂S is added
ZnCl₂+ H₂S ZnS + 2 HCl
Steric hindrance created by “chemical capping”
Chemical capping- high or low temperature
depending on the reactants
High temp reactions- cold organometallic reactants
are injected in solvent like
trioctylphosphineoxide(TOPO) held at > 300ºC
Although it Is a very good method of synthesis, most
organometallic compounds are expensive.
 SOL GEL METHOD

2types of materials or components- “sol” and “gel”

M. Ebelman synthesized them in 1845
Low temperature process- less energy consumption
and less pollution
Generates highly pure, well controlled ceramics
Economical route, provided precursors are not
expensive
Possible to synthesize
nanoparticles, nanorods, nanotubes etc.,
Sols are solid particles in a liquid- subclass of colloids
Gels – polymers containing liquid
The process involves formation of ‘sols’ in a liquid and
then connecting the sol particles to form a network
Liquid is dried- powders, thin films or even monolithic
solid
Particularly useful to synthesize ceramics or metal
oxides
Hydrolysis of precursors condensation

polycondensation
Precursors-tendency to form gels
Alkoxides or metal salts
Oxide ceramics are best synthesized by sol gel route
For ex: in SiO₄, Si is at the centre
and 4 oxygen atoms at the apexes
of tetrahedron
Very ideal for forming sols
By polycondensation process
sols are nucleated and sol-gel is
formed
 ADVANTAGES

Simple techniques
Inexpensive instrumentation
Low temperature (<350ºC)
synthesis
Doping of foreign atoms (ions) is possible during
synthesis
Large quantities of material can be obtained
Variety of sizes and shapes are possible
Self assembly or patterning is possible
BIOLOGICAL
METHODS
 Green synthesis
3 types:
1.Use of microorganisms like fungi, yeats(eukaryotes)
or bacteria, actinomycetes(prokaryotes)
2. Use of plant extracts or enzymes
3.Use of templates like DNA, membranes, viruses and
diatoms
SYNTHESIS USING MICROORGANISMS

Microorganisms are capable of interacting with

metals coming in contact with hem through their cells
and form nanoparticles.
The cell- metal interactions are quite complex
Certain microorganisms are capable of separating
metal ions.
Pseudomonas stuzeri Ag259 bacteria are commonly found
in silver mines.
Capable of accumulating silver inside or outside their cell
walls
Numerous types of silver nanoparticles of different
shapes
can be produced having size <200nm intracellularly
Low concentrations of metal ions (Au⁺,Ag⁺ etc) can be
converted to metal nanoparticles by Lactobacillus strain
present in butter milk.
Fungi – Fusarium oxysporum challenged with gold or
silver salt for app. 3 days produces gold or silver
nanoparticles extracellularly.
Extremophilic actinomycete Thermomonospora sp.
Produces gold nanoparticles extracellularly.
Semiconductor nanoparticles like CdS, ZnS, PbS
etc., can be produced using different microbial
routes.
Sulphate reducing bateria of the family
Desulfobacteriaceae can form 2-5nm ZnS nanoparticle.
Klebsiella pneumoniae can be used to synthesize CdS
nanoparticles.
when [Cd(NO₃)₂] salt is mixed in a solution containing
bacteria and solution is shaken for about1 day at
~38ºC ,CdS nanoparticle in the size range ~5 to 200 nm
can be formed.
SYNTHESIS USING PLANT
EXTRACTS

Leaves of geranium plant ( Pelargonium graveolens)

have been used to synthesize gold nanoparticles
Plant associated fungus- produce compounds such as
taxol and gibberellins
Exchange of intergenic genetics
between fungus and plant.
Nanoparticles produced by fungus and
leaves have different shapes and
sizes.
Nanoparticles obtained using Colletotrichum sp.,
fungus is mostly spherical while thoe obtained from
geranium leaves are rod and disk shaped.
finely crushed leaves
(Erlenmeyer flask)

boiled in water ( 1 min)

cooled and decanted

added to HAuCl₄ aq.

Solution

gold nanoparticles
within a minute
 SYNTHESIS USING DNA

CdS or other sulfide nanoparticles can be synthesized

using DNA.
DNA can bind to the surface of
growing nanoparticles.
ds Salmon sperm DNA can be sheared
to an average
size of 500bp.
Cadmium acetate is added to a
desired medium like water, ethanol,
propanol etc.
Reaction is carried out in a glass flask- facility to purge
the solution and flow with an inert gas like N₂.
Addition of DNA should be made and then Na₂S can
be added dropwise.
Depending on the concentrations of cadmium
acetate, sodium chloride and DNA ,nanoparticles of
CdS with sizes less than ~10 nm can be obtained.
DNA bonds through its negatively charged PO₄ group
to positively charged (Cd⁺) nanoparticle surface.
USE OF PROTEINS, TEMPLATES LIKE
DNA , S- LAYERS ETC

Various inorganic materials such as carbonates,

phosphates, silicates etc are found in parts of bones,
teeth, shells etc.
Biological systems are capable of integrating with
inorganic materials
Widely used to synthesize nanoparticles
 FERRITI
N

Ferritin is a colloidal protein of nanosize.

Stored iron in metabolic process and is abundant in
animals.
Capable of forming 3 dimensional hierarchical
structure.
24 peptide subunits – arranged in such a way that
they create a central cavity of ~6 nm.
Diameter of polypeptide shell is 12 nm.
Ferritin can accommodate 4500 Fe atoms.
Ferritin without inorganic matter in its cavity is called
apoferritin and can be used to entrap desired
nanomaterial inside the protein cage.
Remove iron from ferritin to form apoferritin

Introduce metal ions to form metal nanoparticles

inside the cavity
PROCEDURE TO CONVERT FERRITIN
TO APOFERRITIN

Horse spleen ferritin

diluted with sodium

acetate buffer (placed in
dialysis bag)

sodium+ thioglycolic
acetate acid

dialysis bag kept

under
N₂ gas flow for 2-3
hrs
solution needs to be
replaced from time to time
for 4-5 hrs.

saline for 1 hr

refreshed saline
for 15-20 hrs

APOFERRITIN
APOFERRITIN

mixed with NaCl and N-tris

methyl-2-aminoethanosulphonic
acid (TES)

aq. Cadmium acetate added and

stirred with constant N₂ spurging

aq. Solution of Na₂S is added

twice
with 1 hr interval.
Applications

 Drug delivery systems

 Anti-corrosion barrier coatings
 UV protection gels
 Lubricants and scratch free paints
 New fire retardant materials
 New scratch/abrasion resistant materials
 Superior strength fibres and films